Crystal structure and Hirshfeld surface analysis of ethane-1,2-diaminium 3-[2-(1,3-dioxo-1,3-di­phenyl­propan-2-yl­idene)hydrazin­yl]-5-nitro-2-oxido­benzene­sulfonate dihydrate

Atioğlu, Z.; Akkurt, M.; Toze, F.A.A.; Huseynov, F.E.; Hajiyeva, S.F.

doi:10.1107/S2056989018009118

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 74| Part 7| July 2018| Pages 1021-1025

https://doi.org/10.1107/S2056989018009118

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Crystal structure and Hirshfeld surface analysis of ethane-1,2-diaminium 3-[2-(1,3-dioxo-1,3-diphenylpropan-2-ylidene)hydrazinyl]-5-nitro-2-oxidobenzenesulfonate dihydrate

Zeliha Atioğlu,^a Mehmet Akkurt,^b Flavien A. A. Toze,^c ^* Fatali E. Huseynov ^d and Sarvinaz F. Hajiyeva ^e

^aİlke Education and Health Foundation, Cappadocia University, Cappadocia Vocational College, The Medical Imaging Techniques Program, 50420 Mustafapaşa, Ürgüp, Nevşehir, Turkey, ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^cDepartment of Chemistry, Faculty of Sciences, University of Douala, PO Box 24157, Douala, Republic of , Cameroon, ^dDepartment of Ecology and Soil Sciences, Baku State University, Z. Xalilov Str. 23, Az 1148 Baku, Azerbaijan, and ^eOrganic Chemistry Department, Baku State University, Z. Xalilov Str. 23, Az 1148 Baku, Azerbaijan
^*Correspondence e-mail: toflavien@yahoo.fr

Edited by P. McArdle, National University of Ireland, Ireland (Received 21 June 2018; accepted 22 June 2018; online 28 June 2018)

In the anion of the title hydrated salt, C₂H₁₀N₂²⁺·C₂₁H₁₃N₃O₈S²⁻·2H₂O, the planes of the phenyl rings and the benzene ring of the 5-nitro-2-oxidobenzenesulfonate group are inclined to one another by 44.42 (11), 56.87 (11) and 77.70 (12)°. In the crystal, the anions are linked to the cations and the water molecules by N—H⋯O and O—H⋯O hydrogen bonds, forming a three-dimensional network. Furthermore, there are face-to-face π–π stacking interactions between the centroids of one phenyl ring and the benzene ring of the 5-nitro-2-oxidobenzenesulfonate group [centroid–centroid distance = 3.8382 (13) Å and slippage = 1.841 Å]. A Hirshfeld surface analysis was conducted to verify the contributions of the different intermolecular interactions.

Keywords: crystal structure; 5-nitro-2-oxidobenzenesulfonate group; hydrogen bond; π–π stacking; Hirshfeld surface analysis.

CCDC reference: 1851087

1. Chemical context

Arylhydrazones of β-diketones (AHBD) and their complexes have attracted much attention due to their synthetic potential for organic and inorganic chemistries and diverse useful properties (Gurbanov et al., 2017a ,b ; Jlassi et al., 2014 , 2018 ; Ma et al., 2017a ,b ; Mahmudov & Pombeiro, 2016 ; Mahmudov et al., 2014 , 2017a ,b ). Usually, AHBDs have strong intramolecular resonance-assisted hydrogen bonding (RAHB), which has a more profound effect on their reactivity (Mahmudov et al., 2016) than regular hydrogen bonding and other types of noncovalent interactions (Ledenyova et al., 2018 ; Mahmoudi et al., 2016 , 2018 ; Nasirova et al., 2017 ; Politzer et al., 2017 ; Scheiner, 2013 ; Shixaliyev et al., 2018 ; Vandyshev et al., 2017 ).

Herein we found the strong RAHB and intermolecular charge-assisted hydrogen bonding that was expected in the title hydrated salt ethane-1,2-diaminium 3-[2-(1,3-dioxo-1,3-diphenylpropan-2-ylidene)hydrazinyl]-5-nitro-2-oxidobenzenesulfonate dihydrate.

2. Structural commentary

In the anion of the title salt (Fig. 1), the planes of the phenyl rings (C9–C14 and C16–C21) and the benzene ring (C1–C6) of the 5-nitro-2-oxidobenzenesulfonate group are inclined to one another by 44.42 (11), 56.87 (11) and 77.70 (12)°, respectively. The torsion angles O1—C2—C1—N1, C1—N1—N2—C7, N1—N2—C7—C8, N2—C7—C8—O7, N2—C7—C8—C9, N2—C7—C15—O8, N2—C7—C15—C16, C7—C15—C16—C17 and O8—C15—C16—C17 are 2.7 (3), −178.65 (19), −2.0 (3), −9.5 (3), 166.9 (2), 133.9 (2), −44.9 (3), −21.3 (3) and 159.9 (2)°, respectively. Therefore, the molecular conformation of the title compound is not planar. The values of the geometric parameters of the title compound are within normal ranges (Allen et al., 1987 ).

Figure 1
The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms are shown as spheres of arbitrary radius.

3. Supramolecular features and Hirshfeld surface analysis

In the crystal structure of the title compound, the anions are linked to the cations and two water molecules by N—H⋯O and O—H⋯O hydrogen bonds, forming a three-dimensional network (Table 1 and Fig. 2). Furthermore, there are face-to-face π–π stacking interactions between the centroids of one phenyl ring (atoms C1–C6, Cg1) and the benzene ring of the 5-nitro-2-oxidobenzenesulfonate group (Cg2) [Cg1⋯Cg2^a = 3.8382 (13) Å and slippage = 1.841 Å; symmetry code: (a) x + 1, −y + $[{3\over 2}]$ , z + $[{1\over 2}]$ ].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H10A⋯O8ⁱ	0.85	2.10	2.928 (2)	165
O9—H9A⋯O4	0.85	1.99	2.827 (2)	169
O9—H9B⋯O2ⁱⁱ	0.85	2.03	2.866 (2)	170
O10—H10B⋯O4ⁱⁱⁱ	0.85	2.36	3.139 (3)	152
N1—H1N⋯O7	0.90	1.92	2.568 (2)	127
N4—H4A⋯O1ⁱⁱ	0.90	1.94	2.826 (2)	167
N4—H4B⋯O6^iv	0.90	2.30	2.960 (2)	130
N4—H4B⋯O7ⁱⁱ	0.90	2.24	2.797 (2)	119
N5—H5B⋯O1ⁱⁱ	0.90	2.01	2.864 (2)	158
N4—H4B⋯O6^iv	0.90	2.30	2.960 (2)	130
N4—H4B⋯O7ⁱⁱ	0.90	2.24	2.797 (2)	119
N4—H4C⋯O3	0.90	1.86	2.756 (2)	177
N5—H5A⋯O10ⁱⁱ	0.90	1.98	2.775 (3)	146
N5—H5B⋯O3ⁱⁱ	0.90	2.32	2.778 (2)	112
N5—H5C⋯O9^v	0.90	1.98	2.835 (3)	159
Symmetry codes: (i) $[x+1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x+1, y, z; (iii) -x+1, -y+2, -z+1; (iv) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (v) -x+2, -y+2, -z+1.

Figure 2
A view along the a axis of the packing and hydrogen bonding of the title compound.

The Hirshfeld surface mapped over d_norm (McKinnon et al., 2004 ; Spackman & Jayatilaka, 2009 ) for the title compound is depicted in Fig. 3. The red areas on the surface indicate short contacts as compared to the sum of the van der Waals radii, the blue areas indicate long contacts and the white areas indicate contacts with distances equal to the sum of the van der Waals radii. The highlighted red area shows the O—H⋯O hydrogen bonding, which is responsible for connecting anions and cations to each other.

Figure 3
The Hirshfeld surface of the title compound mapped with d_norm.

The overall two-dimensional fingerprint plot for the title compound and those delineated into O⋯H/H⋯O, H⋯H, C⋯H/H⋯C, C⋯C and C⋯O/O⋯C contacts are illustrated in Fig. 4; the percentage contributions from the different interatomic contacts to the Hirshfeld surfaces are as follows: O⋯H/H⋯O (39.5%), H⋯H (33.8%), C⋯H/H⋯C (14.5%), C⋯C (4.3%) and C⋯O/O⋯C (2.4%). The contributions of the other weak intermolecular contacts to the Hirshfeld surfaces are listed in Table 2. The large number of O⋯H/H⋯O, H⋯H, C⋯H/H⋯C, C⋯C and C⋯O/O⋯C interactions suggest that van der Waals interactions and hydrogen bonding play the greatest roles in the crystal packing (Hathwar et al., 2015 ). A view of the Hirshfeld surface of the title complex plotted over the shape index is given in Fig. 5.

Table 2
Percentage contributions of interatomic contacts to the Hirshfeld surface for the title compound

Contact	Percentage contribution
O⋯H/H⋯H	39.5
H⋯H	33.8
C⋯H/H⋯C	14.5
C⋯C	4.3
C⋯O/O⋯C	2.4
N⋯O/O⋯N	1.8
C⋯N/N⋯C	1.5
N⋯H/H⋯N	1.1
O⋯O	1.1

Figure 4
The two-dimensional fingerprint plots of the title compound, showing (a) all interactions, and delineated into (b) H⋯H, (c) O⋯H/H⋯O, (d) H⋯N/N⋯H, (e) C⋯O/O⋯C and (f) C⋯H/H⋯C interactions [d_e and d_i represent the distances from a point on the Hirshfeld surface to the nearest atoms outside (external) and inside (internal) the surface, respectively].

Figure 5
View of the three-dimensional Hirshfeld surface of the title complex plotted over shape index.

4. Synthesis and crystallization

Synthesis of 3-[2-(1,3-dioxo-1,3-diphenylpropan-2-ylidene)hydrazineyl]-2-hydroxy-5-nitrobenzenesulfonic acid (H₃L) and its characterization by elemental analysis, ¹H/¹³C NMR and IR was reported in Kuznik et al. (2011 ). 469 mg (1 mmol) of H₃L was dissolved in 30 ml of methanol and 0.06 ml (1 mmol) of ethylenediamine was added, with stirring for 5 min at room temperature (rt). The reaction mixture was then kept in air at rt for slow evaporation. After ca 2–3 d, orange crystals of the title compound were formed (yield 84%, based on H₃L). The final product was soluble in acetone, dimethyl sulfoxide (DMSO), ethanol and dimethylformamide (DMF), and insoluble in non-polar solvents. Elemental analysis for C₂₃H₂₇N₅O₁₀S, found (calculated) (%): C 48.79 (48.85), H 4.77 (4.81), N 12.27 (12.38). IR (KBr): 3470 ν(OH), 2989 ν(NH), 1667 ν(C=O), 1613 ν(C=O⋯H), 1576 ν(C=N) cm⁻¹. ¹H NMR (DMSO, internal TMS): δ 3.86 (4H, 2CH₂), 7.32–8.43 (12H, Ar—H), 10.13 (6H, 2NH₃), 14.36 (s, 1H, N—H). ¹³C NMR (DMSO, internal TMS): δ 41.18 (2CH₂), 109.43 (2Ar—H), 123.01 (2Ar—H), 127.72 (2Ar—H), 128.28 (2Ar—H), 130.35 (Ar—H), 132.52 (Ar—H), 132.67 (Ar—H), 132.88 (Ar—H), 133.13 (Ar—H), 133.57 (Ar—CO), 133.80 (Ar—CO), 134.25 (C=N), 137.89 (Ar—SO₃⁻), 143.38 (Ar—NH—N), 146.15 (Ar-NO₂), 160.72 (Ar—O⁻), 191.37 (C=O), 191.89 (C=O).

5. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with O—H = 0.85 Å, N—H = 0.90 Å and C—H = 0.93–0.97 Å, and U_iso(H) = 1.5U_eq(O) and 1.2U_eq(C,N).

Table 3
Experimental details

Crystal data
Chemical formula	C₂H₁₀N₂²⁺·C₂₁H₁₃N₃O₈S²⁻·2H₂O
M_r	565.55
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	7.0590 (6), 23.851 (2), 15.3622 (13)
β (°)	93.337 (3)
V (Å³)	2582.1 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.19
Crystal size (mm)	0.26 × 0.15 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007 )
T_min, T_max	0.946, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	41494, 4930, 3559
R_int	0.083
(sin θ/λ)_max (Å⁻¹)	0.611

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.112, 1.02
No. of reflections	4930
No. of parameters	352
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.34
Computer programs: APEX2 and SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008 ), SHELXL2018 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1851087

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989018009118/qm2125sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018009118/qm2125Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018009118/qm2125Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

Ethane-1,2-diaminium 3-[2-(1,3-dioxo-1,3-diphenylpropan-2-ylidene)hydrazinyl]-5-nitro-2-oxidobenzenesulfonate dihydrate top

Crystal data top

C₂H₁₀N₂²⁺·C₂₁H₁₃N₃O₈S²⁻·2H₂O	F(000) = 1184
M_r = 565.55	D_x = 1.455 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.0590 (6) Å	Cell parameters from 7684 reflections
b = 23.851 (2) Å	θ = 2.7–25.0°
c = 15.3622 (13) Å	µ = 0.19 mm⁻¹
β = 93.337 (3)°	T = 296 K
V = 2582.1 (4) Å³	Plate, orange
Z = 4	0.26 × 0.15 × 0.08 mm

Data collection top

Bruker APEXII CCD diffractometer	3559 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.083
Absorption correction: multi-scan (SADABS; Bruker, 2007)	θ_max = 25.8°, θ_min = 2.7°
T_min = 0.946, T_max = 0.975	h = −8→8
41494 measured reflections	k = −29→29
4930 independent reflections	l = −18→17

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.112	w = 1/[σ²(F_o²) + (0.053P)² + 0.9465P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
4930 reflections	Δρ_max = 0.37 e Å⁻³
352 parameters	Δρ_min = −0.34 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.1741 (3)	0.76729 (8)	0.65426 (13)	0.0333 (5)
C2	0.2217 (3)	0.82248 (8)	0.62626 (12)	0.0288 (4)
C3	0.3962 (3)	0.84445 (8)	0.66401 (12)	0.0299 (4)
C4	0.5152 (3)	0.81269 (10)	0.71878 (13)	0.0375 (5)
H4	0.630239	0.827277	0.740985	0.045*
C5	0.4612 (3)	0.75882 (10)	0.74031 (14)	0.0411 (5)
C6	0.2903 (3)	0.73575 (9)	0.70886 (14)	0.0408 (5)
H6	0.255832	0.699667	0.724575	0.049*
C7	−0.2184 (3)	0.67860 (9)	0.59205 (13)	0.0364 (5)
C8	−0.3471 (3)	0.71352 (9)	0.53687 (14)	0.0374 (5)
C9	−0.5092 (3)	0.68929 (9)	0.48251 (13)	0.0369 (5)
C10	−0.5022 (3)	0.63658 (10)	0.44507 (15)	0.0451 (6)
H10	−0.397420	0.613599	0.456841	0.054*
C11	−0.6522 (4)	0.61810 (11)	0.38988 (17)	0.0572 (7)
H11	−0.646209	0.583020	0.363766	0.069*
C12	−0.8086 (4)	0.65112 (12)	0.37366 (17)	0.0595 (7)
H12	−0.909617	0.638138	0.337620	0.071*
C13	−0.8166 (4)	0.70340 (12)	0.41054 (17)	0.0566 (7)
H13	−0.923465	0.725723	0.399761	0.068*
C14	−0.6665 (3)	0.72290 (10)	0.46357 (15)	0.0450 (6)
H14	−0.670797	0.758854	0.486795	0.054*
C15	−0.2678 (3)	0.62089 (9)	0.62050 (13)	0.0379 (5)
C16	−0.1207 (3)	0.57670 (8)	0.62333 (13)	0.0365 (5)
C17	0.0414 (3)	0.57992 (10)	0.57562 (16)	0.0489 (6)
H17	0.060741	0.611197	0.541097	0.059*
C18	0.1726 (4)	0.53723 (11)	0.57924 (19)	0.0602 (7)
H18	0.278000	0.539226	0.545767	0.072*
C19	0.1484 (4)	0.49156 (11)	0.63225 (18)	0.0587 (7)
H19	0.239317	0.463295	0.635947	0.070*
C20	−0.0099 (4)	0.48781 (10)	0.67960 (16)	0.0499 (6)
H20	−0.025764	0.456967	0.715476	0.060*
C21	−0.1450 (3)	0.52920 (9)	0.67446 (14)	0.0414 (5)
H21	−0.253732	0.525567	0.705362	0.050*
C22	0.8316 (3)	0.90536 (10)	0.39177 (16)	0.0473 (6)
H22A	0.824565	0.944179	0.410147	0.057*
H22B	0.740222	0.900097	0.342811	0.057*
C23	1.0255 (3)	0.89378 (11)	0.36299 (15)	0.0492 (6)
H23A	1.044320	0.853556	0.359854	0.059*
H23B	1.036856	0.909075	0.305023	0.059*
N1	−0.0004 (3)	0.74786 (7)	0.61817 (11)	0.0383 (4)
H1N	−0.064888	0.772475	0.583317	0.046*
N2	−0.0546 (3)	0.69610 (7)	0.62829 (11)	0.0385 (4)
N3	0.5811 (4)	0.72606 (10)	0.79974 (13)	0.0586 (6)
N4	0.7806 (2)	0.86879 (8)	0.46401 (12)	0.0400 (4)
H4A	0.877010	0.865031	0.504591	0.048*
H4B	0.740870	0.835741	0.441351	0.048*
H4C	0.684390	0.883711	0.492181	0.048*
N5	1.1737 (2)	0.91827 (8)	0.42271 (12)	0.0439 (5)
H5A	1.285858	0.920295	0.397881	0.053*
H5B	1.185958	0.899605	0.473641	0.053*
H5C	1.149575	0.954525	0.433951	0.053*
O1	0.11362 (19)	0.84871 (6)	0.57058 (9)	0.0358 (3)
O2	0.3021 (2)	0.94939 (7)	0.66294 (12)	0.0558 (5)
O3	0.4796 (2)	0.91527 (7)	0.54483 (10)	0.0464 (4)
O4	0.6324 (2)	0.92621 (8)	0.68812 (11)	0.0623 (5)
O5	0.7429 (3)	0.74247 (10)	0.81985 (14)	0.0839 (7)
O6	0.5162 (4)	0.68241 (9)	0.83004 (13)	0.0827 (7)
O7	−0.3171 (2)	0.76438 (6)	0.53110 (11)	0.0495 (4)
O8	−0.4290 (2)	0.61161 (7)	0.64236 (12)	0.0555 (5)
O9	0.9258 (2)	0.96664 (7)	0.58733 (11)	0.0505 (4)
H9A	0.846428	0.950189	0.618111	0.076*
H9B	1.031219	0.959099	0.614351	0.076*
O10	0.4185 (3)	0.94367 (8)	0.29341 (12)	0.0612 (5)
H10A	0.441072	0.925449	0.247559	0.092*
H10B	0.432662	0.978519	0.284149	0.092*
S1	0.45667 (7)	0.91402 (2)	0.63830 (3)	0.03736 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0437 (12)	0.0288 (11)	0.0265 (10)	−0.0023 (9)	−0.0048 (9)	0.0007 (8)
C2	0.0316 (10)	0.0282 (10)	0.0261 (10)	0.0006 (8)	−0.0018 (8)	0.0003 (8)
C3	0.0301 (10)	0.0344 (11)	0.0249 (10)	0.0002 (8)	−0.0014 (8)	−0.0032 (8)
C4	0.0336 (11)	0.0518 (14)	0.0264 (11)	0.0056 (10)	−0.0044 (8)	−0.0058 (10)
C5	0.0521 (13)	0.0422 (13)	0.0278 (11)	0.0167 (11)	−0.0074 (10)	0.0016 (9)
C6	0.0630 (15)	0.0269 (11)	0.0314 (11)	0.0034 (10)	−0.0058 (10)	0.0037 (9)
C7	0.0476 (13)	0.0301 (11)	0.0315 (11)	−0.0094 (9)	0.0016 (9)	0.0021 (9)
C8	0.0470 (12)	0.0313 (12)	0.0343 (11)	−0.0081 (9)	0.0062 (9)	0.0000 (9)
C9	0.0461 (12)	0.0358 (12)	0.0292 (11)	−0.0096 (10)	0.0061 (9)	−0.0004 (9)
C10	0.0550 (14)	0.0399 (13)	0.0403 (13)	−0.0071 (11)	0.0027 (11)	−0.0053 (10)
C11	0.0754 (19)	0.0482 (15)	0.0479 (15)	−0.0201 (14)	0.0010 (13)	−0.0089 (12)
C12	0.0593 (17)	0.0687 (19)	0.0493 (16)	−0.0245 (15)	−0.0060 (13)	0.0022 (13)
C13	0.0438 (14)	0.0718 (19)	0.0539 (16)	−0.0033 (13)	0.0015 (12)	0.0090 (14)
C14	0.0511 (14)	0.0435 (13)	0.0409 (13)	−0.0033 (11)	0.0062 (11)	−0.0002 (10)
C15	0.0503 (13)	0.0337 (12)	0.0297 (11)	−0.0117 (10)	0.0021 (9)	0.0032 (9)
C16	0.0492 (12)	0.0280 (11)	0.0319 (11)	−0.0118 (9)	−0.0014 (9)	0.0005 (9)
C17	0.0588 (15)	0.0391 (13)	0.0495 (14)	−0.0103 (11)	0.0094 (12)	0.0042 (11)
C18	0.0558 (16)	0.0540 (17)	0.0721 (19)	−0.0030 (13)	0.0160 (14)	−0.0007 (14)
C19	0.0655 (17)	0.0432 (15)	0.0666 (18)	0.0051 (13)	−0.0044 (14)	−0.0056 (13)
C20	0.0708 (17)	0.0320 (13)	0.0455 (14)	−0.0066 (12)	−0.0066 (12)	0.0025 (10)
C21	0.0564 (14)	0.0310 (12)	0.0366 (12)	−0.0124 (10)	0.0018 (10)	0.0020 (9)
C22	0.0426 (13)	0.0460 (14)	0.0513 (14)	−0.0101 (10)	−0.0159 (11)	0.0175 (11)
C23	0.0549 (15)	0.0589 (15)	0.0330 (12)	−0.0100 (12)	−0.0057 (10)	0.0049 (11)
N1	0.0505 (11)	0.0254 (9)	0.0376 (10)	−0.0106 (8)	−0.0093 (8)	0.0062 (7)
N2	0.0524 (11)	0.0290 (9)	0.0339 (10)	−0.0095 (8)	−0.0003 (8)	0.0043 (8)
N3	0.0747 (16)	0.0610 (15)	0.0377 (12)	0.0342 (13)	−0.0185 (11)	−0.0060 (11)
N4	0.0350 (9)	0.0419 (11)	0.0417 (10)	−0.0091 (8)	−0.0088 (8)	0.0025 (8)
N5	0.0325 (9)	0.0538 (12)	0.0448 (11)	−0.0005 (8)	−0.0036 (8)	0.0119 (9)
O1	0.0338 (7)	0.0317 (8)	0.0402 (8)	−0.0044 (6)	−0.0130 (6)	0.0089 (6)
O2	0.0625 (11)	0.0325 (9)	0.0735 (12)	−0.0020 (8)	0.0133 (9)	−0.0145 (8)
O3	0.0416 (9)	0.0621 (11)	0.0353 (9)	−0.0095 (8)	−0.0007 (7)	0.0085 (7)
O4	0.0527 (10)	0.0841 (14)	0.0479 (10)	−0.0380 (9)	−0.0151 (8)	0.0087 (9)
O5	0.0624 (13)	0.1168 (19)	0.0691 (14)	0.0341 (13)	−0.0251 (11)	0.0068 (13)
O6	0.132 (2)	0.0472 (12)	0.0640 (13)	0.0276 (12)	−0.0364 (13)	0.0117 (10)
O7	0.0617 (10)	0.0296 (9)	0.0552 (10)	−0.0094 (7)	−0.0123 (8)	0.0046 (7)
O8	0.0529 (11)	0.0488 (10)	0.0659 (12)	−0.0097 (8)	0.0134 (9)	0.0171 (9)
O9	0.0475 (9)	0.0469 (10)	0.0573 (10)	−0.0050 (7)	0.0047 (8)	0.0065 (8)
O10	0.0683 (12)	0.0507 (11)	0.0672 (12)	0.0072 (9)	0.0248 (9)	0.0019 (9)
S1	0.0352 (3)	0.0414 (3)	0.0351 (3)	−0.0143 (2)	−0.0016 (2)	−0.0014 (2)

Geometric parameters (Å, º) top

C1—C6	1.365 (3)	C17—H17	0.9300
C1—N1	1.400 (3)	C18—C19	1.377 (4)
C1—C2	1.431 (3)	C18—H18	0.9300
C2—O1	1.276 (2)	C19—C20	1.371 (4)
C2—C3	1.430 (3)	C19—H19	0.9300
C3—C4	1.380 (3)	C20—C21	1.372 (3)
C3—S1	1.764 (2)	C20—H20	0.9300
C4—C5	1.386 (3)	C21—H21	0.9300
C4—H4	0.9300	C22—N4	1.473 (3)
C5—C6	1.387 (3)	C22—C23	1.489 (3)
C5—N3	1.439 (3)	C22—H22A	0.9700
C6—H6	0.9300	C22—H22B	0.9700
C7—N2	1.321 (3)	C23—N5	1.472 (3)
C7—C8	1.466 (3)	C23—H23A	0.9700
C7—C15	1.492 (3)	C23—H23B	0.9700
C8—O7	1.236 (2)	N1—N2	1.305 (2)
C8—C9	1.493 (3)	N1—H1N	0.8999
C9—C10	1.385 (3)	N3—O5	1.230 (3)
C9—C14	1.387 (3)	N3—O6	1.239 (3)
C10—C11	1.389 (3)	N4—H4A	0.9000
C10—H10	0.9300	N4—H4B	0.9000
C11—C12	1.367 (4)	N4—H4C	0.8999
C11—H11	0.9300	N5—H5A	0.8999
C12—C13	1.372 (4)	N5—H5B	0.9000
C12—H12	0.9300	N5—H5C	0.8999
C13—C14	1.379 (4)	O2—S1	1.4468 (17)
C13—H13	0.9300	O3—S1	1.4546 (16)
C14—H14	0.9300	O4—S1	1.4484 (16)
C15—O8	1.225 (3)	O9—H9A	0.8500
C15—C16	1.479 (3)	O9—H9B	0.8498
C16—C21	1.395 (3)	O10—H10A	0.8505
C16—C17	1.396 (3)	O10—H10B	0.8502
C17—C18	1.376 (4)

C6—C1—N1	123.00 (19)	C17—C18—C19	120.2 (3)
C6—C1—C2	123.24 (19)	C17—C18—H18	119.9
N1—C1—C2	113.73 (17)	C19—C18—H18	119.9
O1—C2—C3	124.02 (18)	C20—C19—C18	119.9 (3)
O1—C2—C1	120.68 (17)	C20—C19—H19	120.1
C3—C2—C1	115.29 (17)	C18—C19—H19	120.1
C4—C3—C2	121.70 (19)	C19—C20—C21	120.5 (2)
C4—C3—S1	120.40 (16)	C19—C20—H20	119.7
C2—C3—S1	117.90 (14)	C21—C20—H20	119.7
C3—C4—C5	119.2 (2)	C20—C21—C16	120.6 (2)
C3—C4—H4	120.4	C20—C21—H21	119.7
C5—C4—H4	120.4	C16—C21—H21	119.7
C4—C5—C6	122.05 (19)	N4—C22—C23	112.52 (19)
C4—C5—N3	119.7 (2)	N4—C22—H22A	109.1
C6—C5—N3	118.2 (2)	C23—C22—H22A	109.1
C1—C6—C5	118.4 (2)	N4—C22—H22B	109.1
C1—C6—H6	120.8	C23—C22—H22B	109.1
C5—C6—H6	120.8	H22A—C22—H22B	107.8
N2—C7—C8	124.18 (19)	N5—C23—C22	111.9 (2)
N2—C7—C15	112.46 (19)	N5—C23—H23A	109.2
C8—C7—C15	123.10 (19)	C22—C23—H23A	109.2
O7—C8—C7	119.8 (2)	N5—C23—H23B	109.2
O7—C8—C9	117.9 (2)	C22—C23—H23B	109.2
C7—C8—C9	122.19 (19)	H23A—C23—H23B	107.9
C10—C9—C14	119.0 (2)	N2—N1—C1	121.57 (18)
C10—C9—C8	122.6 (2)	N2—N1—H1N	123.1
C14—C9—C8	118.2 (2)	C1—N1—H1N	115.0
C9—C10—C11	119.8 (2)	N1—N2—C7	120.29 (18)
C9—C10—H10	120.1	O5—N3—O6	122.1 (2)
C11—C10—H10	120.1	O5—N3—C5	119.4 (3)
C12—C11—C10	120.5 (3)	O6—N3—C5	118.5 (2)
C12—C11—H11	119.8	C22—N4—H4A	111.9
C10—C11—H11	119.8	C22—N4—H4B	108.2
C11—C12—C13	120.0 (2)	H4A—N4—H4B	112.8
C11—C12—H12	120.0	C22—N4—H4C	110.6
C13—C12—H12	120.0	H4A—N4—H4C	105.5
C12—C13—C14	120.1 (3)	H4B—N4—H4C	107.8
C12—C13—H13	120.0	C23—N5—H5A	111.6
C14—C13—H13	120.0	C23—N5—H5B	112.0
C13—C14—C9	120.5 (2)	H5A—N5—H5B	110.6
C13—C14—H14	119.8	C23—N5—H5C	111.4
C9—C14—H14	119.8	H5A—N5—H5C	102.2
O8—C15—C16	121.69 (19)	H5B—N5—H5C	108.6
O8—C15—C7	118.9 (2)	H9A—O9—H9B	102.6
C16—C15—C7	119.36 (19)	H10A—O10—H10B	109.4
C21—C16—C17	118.1 (2)	O2—S1—O4	112.35 (11)
C21—C16—C15	119.1 (2)	O2—S1—O3	112.05 (11)
C17—C16—C15	122.75 (19)	O4—S1—O3	112.11 (10)
C18—C17—C16	120.6 (2)	O2—S1—C3	107.09 (10)
C18—C17—H17	119.7	O4—S1—C3	106.34 (10)
C16—C17—H17	119.7	O3—S1—C3	106.41 (9)

C6—C1—C2—O1	175.3 (2)	N2—C7—C15—O8	133.9 (2)
N1—C1—C2—O1	−2.7 (3)	C8—C7—C15—O8	−40.5 (3)
C6—C1—C2—C3	−3.9 (3)	N2—C7—C15—C16	−44.9 (3)
N1—C1—C2—C3	178.05 (17)	C8—C7—C15—C16	140.7 (2)
O1—C2—C3—C4	−174.87 (19)	O8—C15—C16—C21	−19.0 (3)
C1—C2—C3—C4	4.3 (3)	C7—C15—C16—C21	159.75 (19)
O1—C2—C3—S1	5.0 (3)	O8—C15—C16—C17	159.9 (2)
C1—C2—C3—S1	−175.82 (14)	C7—C15—C16—C17	−21.3 (3)
C2—C3—C4—C5	−2.4 (3)	C21—C16—C17—C18	0.1 (3)
S1—C3—C4—C5	177.78 (16)	C15—C16—C17—C18	−178.8 (2)
C3—C4—C5—C6	−0.3 (3)	C16—C17—C18—C19	−2.1 (4)
C3—C4—C5—N3	−177.87 (19)	C17—C18—C19—C20	2.0 (4)
N1—C1—C6—C5	179.35 (19)	C18—C19—C20—C21	0.2 (4)
C2—C1—C6—C5	1.5 (3)	C19—C20—C21—C16	−2.2 (4)
C4—C5—C6—C1	0.8 (3)	C17—C16—C21—C20	2.0 (3)
N3—C5—C6—C1	178.33 (19)	C15—C16—C21—C20	−179.0 (2)
N2—C7—C8—O7	−9.5 (3)	N4—C22—C23—N5	−77.7 (3)
C15—C7—C8—O7	164.2 (2)	C6—C1—N1—N2	−6.5 (3)
N2—C7—C8—C9	166.9 (2)	C2—C1—N1—N2	171.52 (18)
C15—C7—C8—C9	−19.4 (3)	C1—N1—N2—C7	−178.65 (19)
O7—C8—C9—C10	143.6 (2)	C8—C7—N2—N1	2.0 (3)
C7—C8—C9—C10	−32.9 (3)	C15—C7—N2—N1	−172.29 (18)
O7—C8—C9—C14	−31.3 (3)	C4—C5—N3—O5	−11.5 (3)
C7—C8—C9—C14	152.3 (2)	C6—C5—N3—O5	170.9 (2)
C14—C9—C10—C11	−0.4 (3)	C4—C5—N3—O6	167.5 (2)
C8—C9—C10—C11	−175.2 (2)	C6—C5—N3—O6	−10.2 (3)
C9—C10—C11—C12	−1.4 (4)	C4—C3—S1—O2	−123.34 (17)
C10—C11—C12—C13	1.4 (4)	C2—C3—S1—O2	56.81 (18)
C11—C12—C13—C14	0.4 (4)	C4—C3—S1—O4	−3.0 (2)
C12—C13—C14—C9	−2.2 (4)	C2—C3—S1—O4	177.11 (16)
C10—C9—C14—C13	2.1 (3)	C4—C3—S1—O3	116.66 (17)
C8—C9—C14—C13	177.2 (2)	C2—C3—S1—O3	−63.19 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10A···O8ⁱ	0.85	2.10	2.928 (2)	165
O9—H9A···O4	0.85	1.99	2.827 (2)	169
O9—H9B···O2ⁱⁱ	0.85	2.03	2.866 (2)	170
O10—H10B···O4ⁱⁱⁱ	0.85	2.36	3.139 (3)	152
N1—H1N···O7	0.90	1.92	2.568 (2)	127
N4—H4A···O1ⁱⁱ	0.90	1.94	2.826 (2)	167
N4—H4B···O6^iv	0.90	2.30	2.960 (2)	130
N4—H4B···O7ⁱⁱ	0.90	2.24	2.797 (2)	119
N5—H5B···O1ⁱⁱ	0.90	2.01	2.864 (2)	158
N4—H4B···O6^iv	0.90	2.30	2.960 (2)	130
N4—H4B···O7ⁱⁱ	0.90	2.24	2.797 (2)	119
N4—H4C···O3	0.90	1.86	2.756 (2)	177
N5—H5A···O10ⁱⁱ	0.90	1.98	2.775 (3)	146
N5—H5B···O3ⁱⁱ	0.90	2.32	2.778 (2)	112
N5—H5C···O9^v	0.90	1.98	2.835 (3)	159

Symmetry codes: (i) x+1, −y+3/2, z−1/2; (ii) x+1, y, z; (iii) −x+1, −y+2, −z+1; (iv) x, −y+3/2, z−1/2; (v) −x+2, −y+2, −z+1.

Percentage contributions of interatomic contacts to the Hirshfeld surface for the title compound top

Contact	Percentage contribution
O···H / H···H	39.5
H···H	33.8
C···H / H···C	14.5
C···C	4.3
C···O / O···C	2.4
N···O / O···N	1.8
C···N / N···C	1.5
N···H / H···N	1.1
O···O	1.1

Acknowledgements

This work has been partially supported by Baku State University.

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